780 Chemistry Letters Vol.38, No.

8 (2009)

Synthesis of Ordered Cage-like Mesoporous Aluminosilicates

from Na-A Zeolite Precursors Dissolved in HCl
Shunsuke Tanaka,
1;2 Norihito Nakatani,1 and Yoshikazu Miyake1;2
1
Department of Chemical Engineering, Faculty of Engineering, Kansai University,
3-3-35 Yamate-cho, Suita, Osaka 564-8680
2
High Technology Research Center, Kansai University, 3-3-35 Yamate-cho, Suita, Osaka 564-8680

(Received May 12, 2009; CL-090461; E-mail: shun tnk@ipcku.kansai-u.ac.jp)

Highly ordered cubic mesoporous aluminosilicates were
synthesized using PEO106 PPO70 PEO106 triblock copolymer
and aluminosilicate sols containing Si–O–Al bonds, which are
obtained by dissolving Na-A type zeolite in HCl, under mild
acidic conditions (pH 1.9–3.2).
The discovery of ordered mesoporous silicas (MSs) has led
to a considerable interest in the development of various ordered
mesoporous materials.1 The high surface area and large pore
sizes of ordered mesoporous aluminosilicates (MASs) have con-
siderable potential for use as catalysts for conversion of high-
molecular-weight petroleum fractions, which have high diffu-
sion resistance through the micropores of conventional zeolites.
Many research efforts have focused on developing MASs with a
high content of Al tetrahedrally coordinated in the framework
and with high hydrothermal stability. Recently, some methods
for the preparation of MASs with short-range zeolitic building
units have been reported. These methods are based on the use
of protozeolitic nanoclusters, zeolite seeds prepared by a bot-
tom-up approach from zeolite synthesis solutions.2 The zeolite
seeds are presumed to consist of zeolite primary and secondary
structural building subunits, which provide Si–O–Al bonds orig-
inating in zeolite building units.
Li et al. and Yang et al. have reported the synthesis of MASs
using an aluminosilicate ester (sec-BuO)2 AlOSi(OEt)3 .3 Alumi-
nosilicate ester contains two alkoxide functionalities, one on the
Si side and the other on the Al side, which may allow construc-
tion of a continuous Si–O–Al linkage. Inagaki et al. have pre-
pared MCM-41 type MASs containing fragments of the structure
of ZSM-5 zeolite using a filtrate of ZSM-5 dissolved by alkaline
treatment.4 On the other hand, our group has used zeolite LTA
crystals dissolved in a HCl solution as both Al and Si precur-
sors.5 This method proceeds in two steps: (1) zeolite LTA crys-
tals are dissolved in a HCl solution to produce a homogeneous
solution containing Al and Si sources, and (2) a PEO106 -
PPO70 PEO106 triblock copolymer (Pluronic F127) coassembles
with the inorganic species in the presence of an organic base tet-
ess. We also describe the influence of pH on the mesostructure
of products.
In a typical preparation,6 0.5 g of Pluronic F127 was dis-
solved in 130 g of deionized water with stirring at room temper-
ature for 15 min. In parallel with the above procedure, 1 g of zeo-
lite LTA powder was added to 11.2 mL of 2.2–3.0 M HCl solu-
tion, and the mixture was stirred at room temperature for 10 min
to obtain a transparent solution. The LTA-dissolved HCl solu-
tion was added to the aqueous Pluronic F127 solution and then
stirred for an additional 1 h at room temperature. Then, the re-
sulting mixture was aged without stirring at 100  C for 20 h.
The white precipitated product was collected by centrifugation,
washed with deionized water, and then dried in air. Calcination
was performed at 600  C for 5 h to remove the template. The
final products are designated as X-MS or X-MAS, where X is
the pH value of the final solution (shown in Table 1).
The crystal structure of mesoporous materials prepared
using the LTA-dissolved HCl solutions was characterized by
wide-angle XRD. All products show no diffractions attributable
to the LTA structure, indicating that the framework was com-
posed of an amorphous phase. From EDX and ICP analyses, it
was found that 1.4-MS is made of pure silica. The removal of
Al from the zeolite lattice occurs during the dissolution under
strongly acidic conditions. A complete dealumination results
in complete Si–O–Al bond dissociation.7 The LTA-dissolved
HCl solution contains entirely distinct Al and Si species. Thus,
the pure silica framework of 1.4-MS suggests an absence of in-
teraction between the Al species and Pluronic F127. Free Al3þ
could not interact the protonated PEO segments and silicate spe-
cies and could not enter the silica matrix. The calcined 1.4-MS
has an ordered mesostructure with a d spacing of 14.7 nm.
Table 1. Preparation and physicochemical properties of or-
dered mesoporous materials prepared using LTA-dissolved
HCl solutions
HCla d c dp d SBET e VT f
Yieldb Si/Al
/M /nm /nm /m g /cm3 g1
2 1

ramethylammonium hydroxide (TMAOH), followed by hydro- 1.4-MS 3.0 0.31 Al free 14.7 6.6 750 0.57
thermal treatment. We note that the first step mentioned above 1.9-MAS 2.5 0.33 35 17.3 7.7 790 0.73
is very important as it provides a Si–O–Al bond originating from 2.3-MAS 2.4 0.35 19 17.5 8.4 910 0.83
a zeolite building unit. 2.8-MAS 2.3 0.36 13 17.7 8.4 870 0.84
In this study, we have developed two-step synthesis of well- 3.2-MAS 2.2 0.36 9 — 10.3 600 1.03
ordered MASs under relatively mild acidic conditions. In the a
Concentration of HCl solution used for dissolution of LTA zeo-
first step, zeolite nanoblocks are prepared by a top-down ap- lite. b g-Calcined product/g-LTA. c Lattice d spacing. d Pore di-
proach using zeolite crystals by dissolution of LTA in HCl solu- ameter calculated by the Barrett–Joyner–Halenda method using
tion at carefully controlled concentration. In the second step, we adsorption branches. e Brunauer–Emmett–Teller (BET) surface
combine the above solution and aqueous Pluronic F127 solution area. f Total pore volume calculated as the amount of N2 adsorb-
in the absence of TMAOH to carry out the self-assembly proc- ed at a relative pressure of 0.99.

Copyright Ó 2009 The Chemical Society of Japan

Chemistry Letters Vol.38, No.8 (2009)
On the other hand, Al is incorporated into the mesoporous
framework of products prepared under relatively mild acidic
conditions. A decrease in the concentration of HCl resulted in
a decrease in the Si/Al ratio of products, indicating that the
amount of Al species incorporated in the framework had increas-
ed. The incorporation of Al in the silica matrix suggests that the
zeolite nanoblocks retain the local structure of the zeolite. The
aluminosilicate sol containing the Si–O–Al bonds was obtained
by adjusting the HCl concentration and then was used as a sin-
gle-source molecular precursor of Si and Al. Al atoms were fixed
in the zeolite nanoblocks and directly introduced into the meso-
structure along with the nanoblocks. From yield evaluation, it is
conjectured that most of silicates are consumed for formation of
organic–inorganic composites. The SAXS patterns of the cal-
cined products prepared at pH 1.9, 2.3, and 2.8 exhibit a well-de-
fined single reflection peak at low 2
angle, corresponding to a d
spacing of greater than 17 nm, which is larger than that of the
pure silica mesoporous 1.4-MS. The SAXS pattern of the cal-
cined 3.2-MAS shows no reflection peak, indicating a disordered
structure.
The porous structures of the products were investigated by
N2 adsorption/desorption measurements (Figure 1). All prod-
ucts calcined at 600  C show typical type-IV curves with a hys-
teresis loop and sharp capillary condensation, both of which are
ascribed to the uniform large cage-like mesopores. Table 1 sum-
marizes the physical properties of ordered mesoporous materials
prepared using solutions of LTA dissolved in HCl. The Si/Al ra-
tio, d spacing, pore diameter, BET surface area, and pore volume
changed, depending upon the pH of the final solution. With an
increasing pH value, the capillary condensation steps were shift-
ed to higher relative pressures. As revealed by pore size distribu-
tion, the pore size shows a clearly increasing trend with an in-
creasing pH value.
As revealed by TEM image of 2.8-MAS (Figure 2), well-
aligned cage-like mesopores were observed. Note that the
Pluronic F127 has a very broad region in its binary tempera-
ture–concentration phase diagram over which a bcc phase is ob-
tained.8 We speculate that the ordered structure is described by
the bcc, likely Im3m symmetry, which is similar to that of MASs
prepared using TMAOH in our previous study. The lattice con-
stant and pore size are in good agreement with that calculated by
the SAXS and N2 sorption measurements.
The interactions between the inorganic species (I) and or-
ganic template (S) during self-assembly have a significant effect
Figure 1. (Left) N2 adsorption/desorption isotherms and
(Right) pore size distribution of (a) 3.2-, (b) 2.8-, (c) 2.3-,
(d) 1.9-, and (e) 1.4-MAS. The isotherms (a), (b), (c), (d), and
(e) are offset by 0, 400, 800, 1200, and 1600 cc g1 , respectively.
The pore size distributions (a), (b), (c), (d), and (e) are offset by
0, 3, 6, 9, and 12 cc g1 , respectively.
Published on the web (Advance View) June 27, 2009; doi:10.1246/cl.2009.780
781
Figure 2. TEM image of 2.8-MAS. (Scale bar; 100 nm).
on the final mesostructure. The structure-directed assembly of
mesoscopically ordered aluminosilicate by dilute Pluronic
F127 under acidic conditions may occur by a pathway that in-
volves a combination of electrostatic and hydrogen-bonding in-
teractions (S0 Hþ X Iþ ).9 X is the intermediated molecular spe-
cies, Cl. At low pH, positively charged protonated aluminosili-
cate species interact preferentially with the more hydrophilic
PEO segments to promote cooperative self-assembly. At high
pH, the low Hþ concentration results in weaker interactions be-
tween the aluminosilicate precursor and the Pluronic F127.
Thus, the absence of sufficiently strong interactions leads to
the formation of a poorly ordered structure or wormhole-like dis-
ordered structure.
Under acidic conditions, the PPO segments are believed to
exhibit more hydrophobicity than the PEO segments. Hydrogen
bonding weakens with decreasing HCl concentration. The de-
crease in hydrogen bonding at the inorganic–organic interface
may decrease the effective head group area and the interfacial
curvature. In other words, the PEO segments become more hy-
drophobic, resulting in shorter lengths of PEO segments associ-
ated with the inorganic wall, increased hydrophobic domain vol-
umes, and increased final mesopore sizes.
The authors thank Associate Prof. J. Hayashi (Kansai Univ.)
for N2 sorption measurements.
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